2-amino-cinnamoylthiophene azo dyes having aniline, tetrahydroquinoline, or benzomorpholine couplers

ABSTRACT

Disclosed are new disperse azo dyes prepared from 2-amino-cinnamoylthiophene compounds. These dyes give bright blue shades, for example, on polyester, cellulose acetate and other synthetic fibers and exhibit improvements in one or more of such properties as bathochromic shift, fastness to light, sublimation, chlorine, heat, ozone, gas, perspiration, crock, and wash, build, pH stability, bloom resistance, depth of shade, leveling, strike rate, migration, and the like. The dyes have the general formula: ##STR1## wherein each R is a substituent selected for example from alkyl, substituted alkyl, hydroxy, alkoxy, halogen, nitro, alkoxycarbonyl, alkanoyloxy, alkanoyl, cyano, alkylamino, and dialkylamino, R 14  is hydrogen or alkyl, C 1  represents an aniline, tetrahydroquinoline or benzomorpholine coupling component which may be extensively substituted, and each of R 12  and R 13  is hydrogen or a substituent such as acyl, acylamido, alkyl, halogen, and cyano.

This invention relates to new azo disperse azo dyes prepared from 2-amino-cinnamoylthiophene compounds. These dyes give bright blue to green shades, for example, on polyester, cellulose acetate and other synthetic fibers and exhibit improvements in one or more of such properties as bathochromic shift, fastness to light, sublimation, chlorine, heat, ozone, gas, perspiration, crock, and wash, build, pH stability, bloom resistance, depth of shade, leveling, strike rate, migration, and the like.

The new disperse dyes have the formula: ##STR2## wherein each R is a substituent selected from alkyl, hydroxy, alkoxy, carboxy, halogen, nitro, alkoxycarbonyl, alkanoyloxy, alkanoyl, cyano, alkylamino, dialkylamino, and alkyl substituted with 1-3 of halogen, alkoxy, alkanoyl, alkanoyloxy, alkoxycarbonyl, alkanoylamino, cyano, nitro, carbamoyl, alkylcarbamoyl, sulfamoyl, alkylsulfamoyl, and the like; C¹ represents an aniline, tetrahydroquinoline or benzomorpholine coupling component which may be extensively substituted; R¹² and R¹³ are each selected from H, alkyl, alkoxy, acyl, halogen, alkylsulfonyl, alkanoyloxy, SO₂ NH₂, SO₂ NH-alkyl, SO₂ N(alkyl)₂, CONH₂, CONHalkyl, CON(alkyl)₂, arylsulfonyl, alkanoyl, acylamido, aroyl, aryl, alkylthio, arylthio, alkenylthio, alkoxycarbonyl, hydroxyalkylcarbamoyl, cyclohexylthio, SO₃ C₆ H₅, cyano, thiocyano, cyclohexylsulfonyl, cyclohexyl, and preferably alkanoyl, aroyl, alkoxycarbonyl, CONH₂, CONHalkyl, hydroxyalkylcarbamoyl, and alkyl substituted with 1-3 of alkoxy, CN, halogen, SO₂ alkyl, CONHalkyl, alkanoyloxy, or SO₂ NHalkyl; R¹⁴ is hydrogen or alkyl.

Preferred dyes of the invention are those containing one cinnamoyl group, R¹⁴ in that group being hydrogen and any R present being halogen, alkyl, alkoxycarbonyl, hydroxy, nitro, alkoxy, carboxy, alkanoyl, cyano, alkylamino or dialkylamino.

The coupler C¹ is preferably selected from those of the formulae: ##STR3## wherein

R¹ and R² are each selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R⁹ in which X is --CO--, --OCO-- --COO--, or --SO₂ -- and R⁹ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R⁹ also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl;

R³ and R⁴ are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two groups selected from alkyl, --OH, alkoxy, halogen and hydroxy substituted alkyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; straight or branched alkenyl; straight or branched alkyl and such alkyl substituted with 1-3 of the following: hydroxy; halogen; cyano; amino; alkoxy; alkoxyalkoxy, hydroxy-alkoxy; succinimido; glutarimido; phenylcarbamoyl-oxy; phthalimido; phthalimidino; 2-pyrrol-idono; cyclohexyl; phenoxy; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; benzoylsulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula ##STR4## wherein y is --NH--, ##STR5## --O--, --S--, or --CH₂ O--; --S--R¹⁰ wherein R¹⁰ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR6## --OXR⁹ ; --NH--X--R⁹ ; --X--R⁹ ; --CONR¹¹ R¹¹ ; --SO₂ NR¹¹ R¹¹ ; wherein R⁹ and X are as defined above and each R¹¹ is selected from H, alkyl, and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, alkoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyl, and alkanoyloxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy substituted with one or more of alkyl, alkoxy or halogen;

or R³ and R⁴ combined form pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene which, with the nitrogen atom to which it is attached, forms a ring; and

R⁵, R⁶, R⁷ and R⁸ are each selected from hydrogen and alkyl. All of the above alkyl, alkylene, alkenyl, and alkoxy moieties or substituents within the definitions of R¹ through R¹¹ preferably contain up to six carbons.

Preferred couplers C¹ of the above formulae are those in which the various substituents have the following values: R¹ is alkyl, alkoxy, alkanoylamino or alkoxycarbonylamino; R² is hydrogen or an alkyl or alkoxy group; each of R³ and R⁴ is hydrogen, an alkyl group or an alkyl group substituted with 1 to 3 of hydroxy, alkoxy, alkoxyalkoxy, hydroxylkoxy, carbamoyl, alkylcarbamoyl, alkanoylamino, sulfamoyl, alkylsulfamoyl, phenyl, cyclohexyl, 1-(2-pyrollidono), phthalimidino, succinimido, cyano, phenoxy, alkylsulfonyl, phthalimido, o-benzoicsulfimido, triazolylthio, alkylsulfonamido, --SO₂ NHR¹¹, phenylsulfonamido, alkoxycarbonylamino, alkylcarbamoyloxy, alkoxycarbonyl, alkoxycarbonyloxy and ##STR7## wherein Y is --NH--. --CH₂ --O-- or --S--; and each of R⁵ and R⁷ hydrogen or alkyl.

The couplers are prepared by procedures well known in the art as shown in the patent literature, e.g., U.S. Pat. Nos. 2,805,218; 2,827,450; and 2,839,523. The dyes of the present invention are readily prepared, for example, by reacting the known azo dyes derived from 2-amino-5-acetyl thiophene and the aforesaid couplers, with benzaldehyde or a substituted benzaldehyde in acetic acid in the presence of concentrated sulphuric acid.

The invention will be further understood from the following examples.

EXAMPLE 1 ##STR8##

Dye (I) was prepared by diazotizing 5-acetyl-2-amino-3-methoxycarbonyl-thiophene and coupling with N,N-diethyl-m-toluidine in known manner.

A mixture of dye I (2 g.), benzaldehyde (1.5 g.), acetic acid (25 ml.) and concentrated sulphuric acid (5 ml.) was stirred at 100° C. for 1.5 hours. The reaction mixture was poured into dilute ammonium acetate solution, and the product dye (II) filtered off, washed with water and dried. The yield of dye (II) was 2.5 g.

This dye when applied to polyester or its blends by known techniques such as given below, gives bright blue shades with good dyeing and fastness properties.

By using the above procedure with the same diazo compound but with the couplers and benzaldehyde type reactants tabulated below, further dyes of the invention are obtained.

    ______________________________________                                                            Benzaldehyde                                                Coupler            Type Compound                                               ______________________________________                                         N,N--Diethyl-m-toluidine                                                                          4-Chlorobenzaldehyde                                        N,N--Diethylaniline                                                                               Benzaldehyde                                                N,N--Diethyl-m-toluidine                                                                          4-Methylbenzaldehyde                                        N,--Ethyl-o-toluidine                                                                             Benzaldehyde                                                2,5-Dimethyl-N--ethyl                                                                             Benzaldehyde                                                aniline                                                                        N--Ethyl-N--hydroxyethyl                                                                          Benzaldehyde                                                aniline                                                                        N,N--Diethyl-m-toluidine                                                                          4-Carbomethoxy-                                                                benzaldehyde                                                N--Ethyl-2,7-dimethyl                                                                             Benzaldehyde                                                tetrahydroquinoline                                                            N,N--Diethyl-2,5-  Benzaldehyde                                                dimethoxyaniline                                                               N--Ethyl-3,6-dimethyl-                                                                            Benzaldehyde                                                1,4-benzomorpholine                                                            N,N--Diethyl-m-toluidine                                                                          4-Hydroxybenzaldehyde                                       ______________________________________                                    

EXAMPLE 2 ##STR9##

Dye (III) was prepared by diazotising the known 2-amino-3-carbomethoxy-5-acetyl thiophene and coupling with N-ethyl 2,2,4,7-tetramethyl tetrahydroquinoline by the standard procedure.

A mixture of dye (III) (2 g) benzaldehyde (1.5 g), acetic acid (25 ml) and concentrated sulphuric acid (5 ml) was stirred at 100° C. for 1.5 hours. The reaction mixture was poured into cold water and the product dye (IV) filtered off, washed with water and dried. The yield of dye (IV) was 2.2 g.

The dye (IV) obtained when applied to nylon, polyester or other synthetic fibres by known techniques gave bright blue shades with good dyeing and fastness properties.

The dyeing of the fibre material may be carried out for example from an aqueous suspension in the presence of carriers at between about 80° and 100° C., in the absence of carriers between about 100°-130° C., or using the so-called thermofixing process at about 180°-230° C. Printing of the material can be carried out by steaming the goods, printed with the new dyestuffs, in the presence of a carrier at temperatures between 80° and 110° C. or in the absence of a carrier at 110°-140° C., or also by treating the printed material according to the thermofixing process at 180°-230° C.

A typical general procedure by which polyester, e.g., poly(ethylene terephthalate) can be dyed with the present dyes is as follows: The dye cake is dispersed by heating and agitating a dyepot containing the dye cake and methyl cellosolve. When the dyecake has been ground free of lumps and dissolved as much as possible in the methyl cellosolve, 2% based on weight of the fabric of Igepon T-51 and 2.0% based on weight of the fabric of sodium lignin sulfonate from a premixed solution of the two components is added. Sufficient demineralized water is added to make about a 30:1 bath ratio of water to dye and a small amount of `Versene 100` (trade mark--sodium salt of ethylenediamine-tetracetic acid and `Tanalon JDM-72` (trade mark--dye carrier) are added. The pH of the dye bath is adjusted to about 5.0 with acetic acid. The fabric samples (wet-out) are entered into the dyepot and the entire contents thereof entered into a pressure dyeing container. The container is sealed and entered into a High Temperature Launder-Ometer which is heated to 49° C. and rotation thereof started. The temperature of the Launder-Ometer is raised to 129° C. at the rate of about 2.8° C. per minute, and maintained at this temperature for 1 hour. The Launder-Ometer is then cooled, and the fabric samples removed and scoured in demineralized water containing 1 g/l of neutral soap and 1 g/l sodium carbonate. The samples are rinsed in cold demineralized water and dried at 121° C. in a forced air oven.

The following tables show exemplary dyes of the present invention wherein the --OCO-- groups are oriented either --COO-- or --OOC--.

                                      TABLE 1                                      __________________________________________________________________________      ##STR10##                                                                     R     R.sup.1                                                                              R.sup.2                                                                            R.sup.3   R.sup.4         R.sup.12                                                                          R.sup.13                          __________________________________________________________________________     H     H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  H                                 H     H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 CN                                                                           H  COCH.sub.3                        H     H     H   CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  CH.sub.3                          H     H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 OH                                                                           H  OC.sub.2 H.sub.5                  H     H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  Cl Cl                                H     H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 CN                                                                           H  SO.sub.2 CH.sub.3                 H     H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OH                                                                           H  COOCH.sub.3                       H     H     H   CH.sub.2 CH.sub.3                                                                         ##STR11##      H  SO.sub.2 NH.sub.2                 H     H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5                                                           H  SO.sub.2 NHCH.sub.3               4-Cl  H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                            H  SO.sub.2 N(C.sub.2 H.sub.5).s                                                  ub.2                              4-CH.sub.3                                                                           H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 C.sub.6 H.sub.5                                                                       H  CONH.sub.2                        H     H     H   C.sub.6 H.sub.11                                                                          ##STR12##      H  CONHCH.sub.3                      H     H     H   C.sub.6 H.sub.11                                                                         CH.sub.2 CH.sub.2 OH                                                                           H  CON(CH.sub.3).sub.2               H     H     H   C.sub.6 H.sub.11                                                                         CH.sub.2 CH.sub.3                                                                              H  SO.sub.2 C.sub.6 H.sub.5          H     H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  SO.sub.2 C.sub.6 H.sub.5          H     H     H   CH.sub.2 CH.sub.2 OCH.sub.3                                                              CH.sub.2 CH.sub.2 COOCH.sub.3                                                                  H  NHCOCH.sub.3                      H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.2 OH                                                                           CH.sub.3                                                                          OC.sub.6 H.sub.5                  H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.3                                                                              CH.sub.3                                                                          C.sub.6 H.sub.5                   H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  CH.sub.3                                                                          SC.sub.6 H.sub.5                  H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                         ##STR13##      CH.sub.3                                                                          SCH.sub.2 CHCH.sub.2              4-OCOCH.sub.3                                                                        CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 CN                                                                           CH.sub.3                                                                          SC.sub.6 H.sub.11                 H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 Cl                                                                           Cl SO.sub.3 C.sub.6 H.sub.5          H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                             Cl CN                                H     NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub. 3                                                                             Cl SCN                               4-OH  NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 CN                                                                           Cl SCN                               4-Cl  NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  SO.sub.2 C.sub.6 H.sub.11         2-Cl  NHCOCH.sub.3                                                                         CH.sub.3                                                                           H         CH.sub.2 CH.sub.2 CN                                                                           H  SC.sub.2 H.sub.5                  4-NO.sub.2                                                                           NHCOCH.sub.3                                                                         CH.sub.3                                                                           H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                                  H  COC.sub.6 H.sub.5                 H     H     OCH.sub.3                                                                          H         C.sub.6 H.sub.11                                                                               H  COOCH.sub.3                       2-CH.sub.3                                                                           CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2                                                            H  OOCCH.sub.3                       4-NO.sub.2                                                                           NHCOCH.sub.3                                                                         H   H         CH.sub.2 C.sub.6 H.sub.11                                                                      H  CONHCH.sub.2 CH.sub.2 OH          2-Cl  NHCOCH.sub.3                                                                         H   H         CH.sub.2 CH.sub.2 OCH.sub.3                                                                    H  H                                 2-OCH.sub.3                                                                          NHCOCH.sub.3                                                                         H   H                                                                                         ##STR14##      H  H                                 4-OCH.sub.3                                                                          NHCOCH.sub.3                                                                         H   H                                                                                         ##STR15##      H  H                                 3-NO.sub.2                                                                           NHCOCH.sub.3                                                                         H   H                                                                                         ##STR16##      H  H                                 2-OH  NHCOCH.sub.3                                                                         H   H         CH(CH.sub.3)CH.sub.2 CH.sub.3                                                                  H  CH.sub.3                          H     H     CH.sub.3                                                                           H         C.sub.6 H.sub.11                                                                               H  CH.sub.3                          H     H     H   H         CH.sub.2 CH.sub.2 CN                                                                           H  COOC.sub.2 H.sub.5                2-CH.sub.3                                                                           H     H   CH.sub.3  CH.sub.3        H  COOC.sub.2 H.sub.5                4-COOCH.sub.3                                                                        H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  H                                 4-CH.sub.3                                                                           H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 C.sub.6 H.sub.5                                                                       H  CH.sub.2 OC.sub.2 H.sub.5         2-OCH.sub.3                                                                          H     H   CH.sub.2 CH.sub.3                                                                        C.sub.6 H.sub.11                                                                               H  CH.sub.2 CH.sub.2 CN              3-OCH.sub.3                                                                          H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OH                                                                           H  CH.sub.2 SO.sub.2 CH.sub.3        4-OCH.sub.3                                                                          H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  CH.sub.2 COOCH.sub.3              4-COOCH.sub.3                                                                        H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH(OH)CH.sub.2 OH                                                                     H  CH.sub.2 COOCH.sub.3              2-Cl  H     H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 CN                                                                           H  CH.sub.2 CONHCH.sub.3             4-Cl  H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 CN                                                                           H  CH.sub.2 SO.sub.2 NHCH.sub.3                                                   .                                 4-N(CH.sub.3).sub.2                                                                  H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 OH                                                                           H  H                                 2-OH  H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  H                                 3-CN  H     H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5                                                           H  COCH.sub.3                        4-CN  H     H   CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.2 OH                                                                           H  CH.sub.3                          H     H     H   CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  OC.sub.2 H.sub.5                  2-CH.sub.3                                                                           H     H   CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                             Cl Cl                                2-OCH.sub.3                                                                          Cl    Cl  H         CH.sub.2 CH.sub.2 CN                                                                           H  SO.sub.2 CH.sub.3                 H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                         ##STR17##      H  COOCH.sub.3                       H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  SO.sub.2 NH.sub.2                 4-COOCH.sub.3                                                                        CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OH                                                                           H  SO.sub.2 NHCH.sub.3               H     CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 NH.sub.2                                                                     H  SO.sub.2 N(C.sub.2 H.sub.5).s                                                  ub.2                              3-OCH.sub.3                                                                          CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 NH.sub.2                                                                     H  CONH.sub.2                        3-NO.sub.2                                                                           CH.sub.3                                                                             H   CH.sub.2 CH.sub.2 CN                                                                     CH.sub.2 CH.sub.2 NH.sub.2                                                                     H  CONHCH.sub.3                      H     NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  CON(CH.sub.3).sub.2               H     NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  H  SO.sub.2 C.sub.6 H.sub.5          H     NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                        (CH.sub.2 CH.sub.2 O).sub.2 CH.sub.2 CH.sub.3                                                  H  SO.sub.2 C.sub.6 H.sub.5          4-N(C.sub.2 H.sub.5).sub.2                                                           NHCOC.sub.6 H.sub.5                                                                  H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 CONH.sub.2                                                                   H  NHCOCH.sub.3                      H     NHCOC.sub.6 H.sub.5                                                                  CH.sub.3                                                                           H         CH.sub.2 CH.sub.3                                                                              CH.sub.3                                                                          OC.sub.6 H.sub.5                  H     NHCOCH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              CH.sub.3                                                                          C.sub.6 H.sub.5                   2-CH.sub. 3                                                                          NHCOCH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  CH.sub.3                                                                          SC.sub.6 H.sub.5                  4-CH.sub.3                                                                           NHCOCH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH(OH)CH.sub.3                                                                        CH.sub.3                                                                          SCH.sub.2 CHCH.sub.2              2-OCH.sub.3                                                                          NHCOCH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.2 CH.sub.2 OH                                                                     CH.sub.2 CH.sub.2 OH                                                                           CH.sub.3                                                                          SC.sub.6 H.sub.11                 2-OH  NHCOCH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.2 CH.sub.2 OCOCH.sub.3                                                            CH.sub.2 CH.sub.2 OCOCH.sub.3                                                                  Cl SO.sub.3 C.sub.6 H.sub.5          4-CO.sub.2 CH.sub.3                                                                  NHCOCH.sub.3                                                                         OCH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                        C.sub.6 H.sub.11                                                                               Cl CN                                2-Cl  NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                         ##STR18##      Cl SCN                               4-Cl  NHCOCH.sub.3                                                                         H   CH.sub.2 CH.sub.3                                                                         ##STR19##      Cl SCN                               4-Cl  CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  COOCH.sub.3                       4-CH.sub.3                                                                           CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  COOCH.sub.3                       H     H     CH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  COOCH.sub.3                       H     CH.sub.3                                                                             CH.sub.3                                                                           H         CH.sub.2 CH.sub.3                                                                              H  COOCH.sub.3                       4-COOH                                                                               CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  COOCH.sub.3                       4-OH  CH.sub.3                                                                             H   CH.sub.2 CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  CONH.sub.2                        __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________      ##STR20##                                                                     R      R.sup.1, R.sup.2, R.sup.5, R.sup.6, R.sup.7, R.sup.8                                          R.sup.3         R.sup.12                                                                          R.sup.13                              __________________________________________________________________________     H      2,7-di-CH.sub.3                                                                               C.sub.2 H.sub.4 OH                                                                             H  H                                     H      2,5-di-CH.sub.38-OCH.sub.3                                                                    CH.sub.2 CH(OH)CH.sub.2 OH                                                                     H  COCH.sub.3                            H      2,2,4,7-tetra-CH.sub.3                                                                        C.sub.2 H.sub.4 CONH.sub.2                                                                     H  CH.sub.3                              H      2,2,4-tri-CH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3                                                                   H  OC.sub.2 H.sub.5                      H      2-CH.sub.37-NHCOCH.sub.3                                                                      C.sub.2 H.sub.4 CN                                                                             Cl Cl                                    2-CH.sub.3                                                                            2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                              C.sub.2 H.sub.4 Cl                                                                             H  SO.sub.2 CH.sub.3                     4-OCH.sub.3                                                                           2-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                            C.sub.2 H.sub.4 OCOCH.sub.3                                                                    H  COOCH.sub.3                           H      7-CH.sub.3     C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                               H  SO.sub.2 NH.sub.2                     2-Cl   2,2,4-di-CH.sub.35,8-di-OCH.sub.3                                                             C.sub.2 H.sub.4 NHCOCHCH.sub.2                                                                 H  CON(CH.sub.3).sub.2                   4-Cl   2,2,4-tri-CH.sub.38-OCH.sub.3                                                                 CH.sub.2 C.sub.6 H.sub.5                                                                       H  SO.sub.2 C.sub.6 H.sub.5              4-CO.sub.2 C.sub.2 H.sub.5                                                            2-CH.sub.37-NHCOCH.sub.3                                                                      C.sub.2 H.sub.4 CONHCH.sub.2 OH                                                                H  SO.sub.2 C.sub.6 H.sub.5              4-Br   2,7-di-CH.sub.3                                                                               C.sub.2 H.sub.5 CH.sub.3                                                                          OC.sub.6 H.sub.5                      2-CN   2,5-di-CH.sub.38-OCH.sub.3                                                                    C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                              CH.sub.3                                                                          C.sub.6 H.sub.5                       4-OCH.sub.3                                                                           2,2,4,7-tetra-CH.sub.3                                                                        C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                                     CH.sub.3                                                                          SC.sub.6 H.sub.5                      4-OH   2,2,4-tri-CH.sub.3                                                                            C.sub.2 H.sub.4 SCH.sub.3                                                                      CH.sub.3                                                                          SCH.sub.2 CHCH.sub.2                  2-OH   2-CH.sub.37-NHCOCH.sub.3                                                                       ##STR21##      CH.sub.3                                                                          SC.sub.6 H.sub.11                     2-NO.sub.2                                                                            2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                               ##STR22##      Cl SO.sub.3 C.sub.6 H.sub.5              H      2,2,4-tri-CH.sub.37-NHCOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.5 Cl CN                                    H      2-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                             ##STR23##      Cl SCN                                   H      7-CH.sub.3                                                                                     ##STR24##      Cl SCN                                   4-NO.sub.2                                                                            3-CN7-CH.sub.3                                                                                 ##STR25##      H  SO.sub.2 C.sub.6 H.sub.11             H      3-CONH.sub.27-CH.sub.3                                                                         ##STR26##      H  SC.sub.2 H.sub.5                      4-N(CH.sub.3).sub.2                                                                   3-Cl7-CH.sub.3                                                                                 ##STR27##      H  COC.sub.6 H.sub.5                     4-N(C.sub.2 H.sub.5).sub.2                                                            3-OCH.sub.37-CH.sub.3                                                                          ##STR28##      H  COOCH.sub.3                           4-CH.sub.3 CO                                                                         2,2,4-di-CH.sub.35,8-di-OCH.sub.3                                                              ##STR29##      H  OOCCH.sub.3                           2-NO.sub.2                                                                            2,2,4-tri-CH.sub.38-OCH.sub.3                                                                  ##STR30##      H  CONHCH.sub.2 CH.sub.2 OH              4-Cl   2-CH.sub.37-NHCOCH.sub.3                                                                       ##STR31##      H  H                                     4-CH.sub.3                                                                            3-OH7-CH.sub.3                                                                                 ##STR32##      H  H                                     2-CH.sub.3                                                                            2,7-di-CH.sub.3                                                                                ##STR33##      H  H                                     3-CH.sub.3                                                                            2,5-di-CH.sub.38-OCH.sub.3                                                                     ##STR34##      H  H                                     4-OCH.sub.3                                                                           2,2,4,7-tetra-CH.sub.3                                                                         ##STR35##      H  CH.sub.3                              4-CN   2,2,4-tri-CH.sub.3                                                                             ##STR36##      H  H                                     H      2-CH.sub.37-NHCOCH.sub.3                                                                       ##STR37##      H  COOC.sub.2 H.sub.5                    H      2,2,4-tri-CH.sub.37-NHCOCH.sub.3                                                               ##STR38##      H  H                                     H      2-CH(CH.sub.3).sub.27-NHCOCH.sub.3                                                             ##STR39##      H  H                                     H      7-CH.sub.3                                                                                     ##STR40##      H  CH.sub.2 OC.sub.2 H.sub.5             H      3-CN7-CH.sub.3 C.sub.2 H.sub.4 OH                                                                             H  CH.sub.2 CH.sub.2 CN                  H      3-CONH.sub.27-CH.sub.3                                                                         ##STR41##      H  CH.sub.2 SO.sub.2 CH.sub.3            H      2,2,4,7-tetra-CH.sub.3                                                                         ##STR42##      H  CH.sub.2 COOCH.sub.3                  H      2,2,4,7-tetra-CH.sub.3                                                                         ##STR43##      H  CH.sub.2 OOCH.sub.3                   2-Cl   2,7-di-CH.sub.3                                                                               C.sub.2 H.sub.4 OCOCH.sub.3                                                                    H  COOCH.sub.3                           4-Cl   2,2,4,7-tetra-CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              H  CONHC.sub.2 H.sub.4 OH                H      2,2,4,7-tetra-CH.sub.3                                                                        CH.sub.2 CH.sub.3                                                                              CH.sub.3                                                                          COOC.sub.2 H.sub.5                    __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________      ##STR44##                                                                     R      R.sup.1, R.sup.2, R.sup.5                                                                 R.sup.3           R.sup.12                                                                          R.sup.13                                __________________________________________________________________________     H      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 OH                                                                               H  H                                       H      3-CH.sub.3 CH.sub.2 CH(OH)CH.sub.2 OH                                                                       H  COCH.sub.3                              H      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 CONH.sub.2                                                                       H  CH.sub.3                                H      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3                                                                     H  OC.sub.2 H.sub.5                        H      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 CN                                                                               Cl Cl                                      H      3-CH.sub.3 C.sub.2 H.sub.4 Cl                                                                               H  SO.sub.2 CH.sub.3                       H      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 OOCC.sub.2 H.sub.5                                                               H  COOCH.sub.3                             H      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                                 H  SO.sub.2 NH.sub.2                       H      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 CONHC.sub.2 H.sub.5                                                              H  SO.sub.2 NHCH.sub.3                     H      3-CH.sub.3 C.sub.2 H.sub.4 CONHC.sub.2 H.sub.5                                                              H  SO.sub.2 N(C.sub.2 H.sub.5).sub.2       H      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 CONHCH.sub.2 C.sub.6 H.sub.5                                                     H  CONH.sub.2                              H      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                               H  CONHCH.sub.3                            H      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 NHCOCHCH.sub.2                                                                   H  CON(CH.sub.3).sub.2                     H      3-CH.sub.3 CH.sub.2 C.sub.6 H.sub.5                                                                         H  SO.sub.2 C.sub.6 H.sub.5                H      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 CONHCH.sub.2 OH                                                                  H  SO.sub.2 C.sub.6 H.sub.5                H      6-NHCOCH.sub.3                                                                            C.sub.3 H.sub.6 NHCONHC.sub.2 H.sub.5                                                            CH.sub.3                                                                          NHCOCH.sub.3                            H      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.5   CH.sub.3                                                                          OC.sub.6 H.sub.5                        H      3-CH.sub.3 C.sub.2 H.sub. 4 SO.sub.2 NH.sub.2                                                               CH.sub.3                                                                          C.sub.6 H.sub.5                         H      3-CH.sub.36-NHCOCH.sub.3                                                                  C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                                       CH.sub.3                                                                          SC.sub.6 H.sub.5                        H      6-NHCOCH.sub.3                                                                            C.sub.2 H.sub.4 SCH.sub.3                                                                        CH.sub.3                                                                          SCH.sub.2 CHCH.sub.2                    H      3,6-di-CH.sub.3                                                                            ##STR45##        CH.sub.3                                                                          SC.sub.6 H.sub.11                       2-CH.sub.3                                                                            3-CH.sub.3                                                                                 ##STR46##        Cl SO.sub.3 C.sub.6 H.sub.5                4-CH.sub.3                                                                            3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR47##        Cl CN                                      2-OCH.sub.3                                                                           6-NHCOCH.sub.3                                                                             ##STR48##        Cl SCN                                     4-OCH.sub.3                                                                           3,6-di-CH.sub.3                                                                            ##STR49##        Cl SCN                                     2-NO.sub.2                                                                            3-CH.sub.3                                                                                 ##STR50##        H  SO.sub.2 C.sub.6 H.sub.11               4-NO.sub.2                                                                            3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR51##        H  SC.sub.2 H.sub.5                        2-Cl   6-NHCOCH.sub.3                                                                             ##STR52##        H  COC.sub.6 H.sub.5                       2-OH   3,6-di-CH.sub.3                                                                            ##STR53##        H  COOCH.sub.3                             4-N(CH.sub.3).sub.2                                                                   3-CH.sub.3                                                                                 ##STR54##        H  OOCCH.sub.3                             4-N(C.sub.2 H.sub.5).sub.2                                                            3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR55##        H  CONHCH.sub.2 CH.sub.2 OH                4-COCH.sub.3                                                                          6-NHCOCH.sub.3                                                                             ##STR56##        H  H                                       4-COOCH.sub.3                                                                         3,6-di-CH.sub.3                                                                            ##STR57##        H  H                                       4-COOC.sub.2 H.sub.5                                                                  3-CH.sub.3                                                                                 ##STR58##        H  H                                       2-CN   3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR59##        H  H                                       4-CN   6-NHCOCH.sub.3                                                                             ##STR60##        H  CH.sub.3                                2-OCH.sub.3                                                                           3,6-di-CH.sub.3                                                                            ##STR61##        H  CH.sub.3                                4-OCH.sub.3                                                                           3-CH.sub.3                                                                                 ##STR62##        H  COOC.sub.2 H.sub.5                      H      3-CH.sub.36-NHCOCH.sub.3                                                                   ##STR63##        H  COOC.sub.2 H.sub.5                      H      6-NHCOCH.sub.3                                                                             ##STR64##        H  H                                       H      3,6-di-CH.sub.3                                                                           C.sub.2 H.sub.4 OH                                                                               H  CH.sub.2 OC.sub.2 H.sub.5               H      3-CH.sub.3                                                                                 ##STR65##        H  CH.sub.2 CH.sub.2 CN                    H      3,6-di-CH.sub.3                                                                            ##STR66##        H  CH.sub.2 SO.sub.2 CH.sub.3              H      3,6-di-CH.sub.3                                                                           CH.sub.2 CH.sub.2 CN                                                                             H  CH.sub.2 COOCH.sub.3                    __________________________________________________________________________

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

I claim:
 1. A compound having the formula ##STR67## in which each R is a group selected from alkyl, hydroxy, alkoxy, carboxy, halogen, nitro, alkoxycarbonyl, alkanoyloxy, alkanoyl, alkylamino, cyano, dialkylamino, and alkyl substituted with 1-3 of halogen, alkoxy, alkanoyl, alkanoyloxy, alkoxycarbonyl, alkanoylamino, cyano, nitro, carbamoyl, alkylcarbamoyl, sulfamoyl, or alkylsulfamoyl; each R¹² is selected from H, alkyl, alkoxy, acyl, halogen, alkylsulfonyl, alkanoyloxy, SO₂ NH₂, SO₂ NHalkyl, SO₂ N(alkyl)₂, CONH₂, CONHalkyl, CON(alkyl)₂, arylsulfonyl, alkanoyl, alkanoylamino, aroyl, aryl, alkylthio, arylthio, alkenylthio, alkoxycarbonyl, hydroxyalkylcarbamoyl, cyclohexylthio, SO₃ C₆ H₅, cyano, thiocyano, cyclohexylsulfonyl, cyclohexyl, and alkyl substituted with 1-3 of alkoxy, CN, halogen, SO₂ alkyl, CONHalkyl or SO₂ NHalkyl; each R¹⁴ is hydrogen or alkyl; and C¹ is an aniline, tetrahydroquinoline, or benzomorpholine azo type dye coupler selected from ##STR68## wherein: R¹ and R² are each selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R⁹ in which X is --CO--, --OOC--, --COO--, or --SO₂ -- and R⁹ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, and when X is --CO--, R⁹ is also selected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, aryl, or furyl;R³ and R⁴ are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two groups selected from alkyl, --OH, alkoxy, halogen and hydroxy substituted alkyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; straight or branched alkenyl; straight or branched alkyl and such alkyl substituted with 1-3 of the following: hydroxy; halogen; cyano; amino; alkoxy; hydroxyalkoxy; succinimido; glutarimido; phenylcarbamoyloxy; phthalimido, phthalimidino; 2-pyrrolidono; cyclohexyl; phenoxy; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; benzoylsulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula ##STR69## wherein Y is --NH--, ##STR70## --O--, --S--, or --CH₂ O--; --S--R¹⁰ wherein R¹⁰ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR71## --OXR⁹ ; --NH--X--R⁹ ; --X--R⁹ ; --CONR¹¹ R¹¹ ; --SO₂ NR¹¹ R¹¹ ; wherein R⁹ and X are as defined above and each R¹¹ is selected from H, alkyl, and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, alkoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyl, and alkanoyloxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy substituted with one or more of alkyl, alkoxy or halogen; or R³ and R⁴ combined form pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene which, with the nitrogen to which it is attached, forms a ring; and R⁵, R⁶, R⁷ and R⁸ are each selected from hydrogen and alkyl.
 2. A dye compound according to claim 1 wherein the coupler has the formula ##STR72## wherein R¹, R², R³, R⁵, R⁶, R⁷, and R⁸ are as defined therein.
 3. A compound of claim 1 wherein: R¹² and R¹³ are each selected from alkanoyl, aroyl, alkoxycarbonyl, CONH₂, CONHalkyl, hydroxyalkylcarbamoyl, and alkyl substituted with 1-3 of alkoxy, CN, halogen, SO₂ alkyl, CONHalkyl, alkanoyloxy or SO₂ NHalkyl;R¹ is alkyl, alkoxy, alkanoylamino, or alkoxycarbonylamino; R² is hydrogen, alkyl, or alkoxy; R³ and R⁴ are the same or different and selected from hydrogen, alkyl and alkyl substituted with 1 to 3 of hydroxy, alkoxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, alkylcarbamoyl, alkanoylamino, sulfamoyl, alkylsulfamoyl, phenyl, cyclohexyl, 1-(2-pyrrolidono), phthalimidino, succinimido, cyano, phenoxy, alkylsulfonyl, phthalimido, o-benzoicsulfimido, triazolylthio, alkylsulfonamido, --SO₂ NHR¹¹, phenylsulfonamido, alkoxycarbonylamino, alkylcarbamoyloxy, alkoxycarbonyl, alkoxycarbonyloxy, ##STR73## and R⁵ and R⁷ are each hydrogen or alkyl.
 4. A dye compound according to claim 1 wherein the coupler has the formula ##STR74## wherein R¹, R², R³ and R⁵ are as defined therein.
 5. The compound of claim 1 having the formula ##STR75##
 6. The compound of claim 1 having the formula ##STR76##
 7. The compound of claim 1 having the formula ##STR77##
 8. The compound of claim 1 having the formula ##STR78##
 9. The compound of claim 1 having the formula: ##STR79## 